Novel silicone compound, and a makeup containing this compound

ABSTRACT

[Aim]This invention relates to a makeup containing a specific modified silicone obtained by an economical manufacturing method not requiring an esterification catalyst, having a high reaction rate and therefore leaving little unreacted material, and in particular relates to a makeup with good skin adhesion, good retention and excellent emulsion stability.  
     [Composition] 
     A silicone compound represented by the general formula (1):  
     
       R 
       1 
       a 
       R 
       2 
       b 
       SiO (4—a—b)/ 
       2  
     
     (in the formula, R 1  is at least one substituent group having 1-30 carbon atoms, chosen from alkyaryl, aralkyl, fluorine-substituted alkyl or organopolysiloxanylsilyl, R 2  is a carboxylate residue represented by the following general formula (2):  
                 
 
     R 3 is a saturated or unsaturated hydrocarbon group having 2-30 carbon atoms, a is 1.0-2.5, and b is 0.001-1.5.

FIELD OF THE INVENTION

[0001] This invention relates to a makeup containing a specific modifiedsilicone obtained by an economical manufacturing method not requiring anesterification catalyst, having a high reaction rate and thereforeleaving little unreacted material, and in particular to a makeup withgood skin adhesion, good retention and excellent emulsion stability.

[BACKGROUND OF THE INVENTION]

[0002] In general, male secretions such as sweat, tears and sebum, leadto messy makeup, and sebum secreted from the skin becomes mixed with theoil in which the makeup is blended. This is a major reason why too muchwetting of the powder in the makeup leads to messy makeup. To reduce theoil in makeup remaining on the skin, it has been attempted to usevolatile oils, such as octamethylcylotetrasiloxane anddecamethylcyclopentasiloxane, as part of the blended oils.

[0003] Friction and water, etc., are external factors which impairmakeup retention. To improve the poor makeup retention which occurs dueto water-soluble substances, such as sweat and tears, loss ofwater-soluble components and sebum, etc., in the skin is prevented, andthe protective effect of the skin is maintained, by blending withsilicone oils which increase water repellent properties.

[0004] Since they have the characteristic features of light feel,outstanding water-repellent properties and high safety, silicone oilssuch as dimethylpolysiloxane for example are being used profusely inmakeup oils in recent years.

[0005] Although dimethylpolysiloxanes have excellent properties as oilsfor use in cosmetics, it cannot be said that significant improvementshad been made regarding enhanced water repellency and adhesion to theskin when they were used in makeup.

[0006] In skin care products also, oils were desired with a light feel,water repellent properties and ease of use which would impart a feelingof adhesion to the skin.

[0007] In the prior art, resins such as rosin or rosin esters purifiedfrom well-known resins for example are occasionally used to improve theadhesion in cosmetics, but they have poor solubility in silicone oilsand it was difficult to blend them with makeup using silicone as afoundation material.

[0008] For example, in Patent No. 2,610,496 (Koho), 2,665,799 (Koho) and2,750,748 (Koho), a makeup is disclosed using the silicone derivative ofa hydrate of abietic acid which is contained in rosin to the extent ofabout 60%. The tetrahydroabietic acid-modified silicone in these patentsis synthesized-by:

[0009] 1) a reaction between an alcohol-denatured silicone andtetrahydroabietic acid or tetrahydroabietic acid chloride, or

[0010] 2) an addition reaction between an ester of tetrahydroabieticacid, an allylpolyoxyethylene alcohol and hydrogen polysiloxane,

[0011] but the step for synthesizing tetrahydroabietic acid chloride,and the reactions between tetrahydroabietic acid and alcohol-denaturedsilicone or allylpolyoxyethylene alcohol are all reactions performedunder acid conditions, and when resin acids are used containing a largeamount of an unsaturated tricyclic diterpene carboxylic acid such asabietic acid, polymerization may occur giving an extreme coloration, andresulting in an alcohol insoluble substance. Therefore, when using thistype of reaction, it was necessary to first perform a hydrogen additionreaction to give a saturated resin acid as described in the abovepatents. Further, when an acid catalyst was used, subsequent steps suchas rinsing with water were necessary after the reaction, so the methodof synthesis could not be described as economical. Therefore, a methodwas desired which could simply and cheaply synthesize abieticacid-modified silicones by direct reaction of rosin, which is anunsaturated tricyclic diterpene carboxylic acid, by a reaction not usingan acid catalyst.

[Problems which this Invention Attempts to Solve]

[0012] It is therefore an object of this invention to provide a methodof synthesizing a silicone compound more cheaply and economically thanin the prior art by the heat addition reaction of an unsaturated orunsaturated carboxylic acid having 2-30 carbon atoms, and an alicyclicepoxy compound. The modified silicone obtained by this method does notgive rise to alcohol insoluble substances, produces little coloration,and does not use an acid catalyst. Further, makeup which uses thismodified silicone are extremely water repellent and have excellentadhesion, while at the same time, it is soluble in volatile oils such asoctamethylcylotetrasiloxane and decamethylcyclopentasiloxane, and istherefore easy to use as a cosmetic oil. Moreover, such makeup has alighter feel than makeup using prior art resins. When this siliconecompound is used as an oil in emulsion systems, it has excellentmiscibility with oils used in ordinary cosmetics such as silicone oils,ester oils and triglycerides.

[Means for Solving the Problems]

[0013] The main object of this invention is a silicone compoundrepresented by the general formula (1):

R ¹ _(a) R ² _(b) SiO _((4—a—b)/2)

[0014] (in the formula, R¹ is at least one substituent group having 1-30carbon atoms chosen from alkyl, aryl, aralkyl, fluorine-substitutedalkyl or organopolysiloxanylsilyl, R² is a carboxylate residuerepresented by the following general formula (2),

[0015] R³ is a saturated or unsaturated hydrocarbon group having 2-30carbon atoms, a is 1.0-2.5, and b is 0.001-1.5.

[0016] Another object of this invention is the above-mentioned siliconecompound wherein R³ is a tricyclic diterpene carboxylic acid. Yetanother object of this invention is the above-mentioned siliconecompound wherein at least part of R¹ is represented by the followinggeneral formula (3)

[0017] (in the formula, R⁴ may respectively be identical or different,and is at least one substituent group having 1-30 carbon atoms chosenfrom alkyl, aryl, aralkyl, fluorine substituted alkyl or hydroxyl, c is1-5, and d is 0-500).

[0018] Another object of this invention is a makeup containing 0.1-99.5weight % of the aforesaid silicone compound and 0.5-99.9 weight % ofoil, and skin care products, hairdressing products, antiperspirant,makeup products, and ultraviolet defense products which partly containthis makeup material. It may also be in the form of a liquid, emulsion,cream, solid, paste, gel, powder, laminate, mousse or spray.

[0019] Yet another object of this invention is a method to synthesizeany of the aforesaid silicone compounds by synthesizing an alicyclicepoxy-modified silicone by an addition reaction of a main chain siloxanesuch as an organohydrogenpolysiloxane to a vinyl alicyclic epoxide, andreacting these with a saturated or unsaturated carboxylic acid.

Embodiments

[0020] The silicone compound a) of this invention may be represented bythe general formula (1).

R ¹ _(a) R ² _(b) SiO _((4—a—b)/2)

[0021] In the formula, a is 1.0-2.5 but preferably 1.2-2.3, and b is0.001-1.5 but preferably 0.05-1.0. R¹ is at least one substituent grouphaving 1-30 carbon atoms, chosen from alky, aryl, aralkyl,fluorine-substituted alkyl or organopolysiloxanylsilyl alkyl.

[0022] R¹ may be an alkyl group such as methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl or decyl; a cycloalkyl group such ascyclopentyl or cyclohexyl; an aryl group such as phenyl or tolyl; anaralkyl group such as benzyl or phenetyl; an alcohol residue such asolioxy or alioxy; a fluorinated alkyl group such as trifluoropropyl orheptadecafluorodecyl, and organopolysiloxanylsilyl alkyl represented bythe following general formula (3).

[0023] It is preferable that at least about 80% of R are methyl groups.Moreover, it is preferable that at least part of R¹ is theorganopolysiloxanylsilyl alkyl group represented by the above-mentionedgeneral formula (3). In the above formula (3), R⁴ may respectively beidentical or different, and is at least one substituent group having1-30 carbon atoms chosen from alkyl, aryl, aralkyl, fluorine-substitutedalkyl or hydroxyl, and c is 1-5. In particular, when synthesizing thissubstituent from the reaction of a vinyl group and a SiH group, c is 2,and d is 0-500 but preferably 1-100.

[0024] When d is larger than 500, problems such as poor reactivity ofthe main chain may arise.

[0025] The silicone compound a) represented by the general formula (1)is synthesized by an equilibrium reaction using an acid or alkalicatalyst according to standard methods. The branch silicone unit in thissilicone compound is introduced by using a trialkoxymethylsilane,trihydroxymethylsilane, tris (trimethylsiloxy) methylsilane and theirstraight chain or cyclic polymers for the equilibrium reaction, orbranched by performing a ring opening polymerization with a livingpolymerization catalyst using a silanol-denatured silicone.

[0026] The silicone which is branched by the organopolyxsiloxanylalkylgroup shown by the general formula (3) can be synthesized by an additionreaction of an organohydrogen polysiloxane to a single-terminated vinyldenatured organopolysiloxane or vinyl denaturated organosilanerepresented by the following general formula (4).

[0027] R² is a carboxylate residue represented by the following generalformula (2).

[0028] In the formula, R³ is a saturated or unsaturated hydrocarbongroup having 2-30 carbon atoms, preferably a resin acid residue such asacetic acid, butyric acid, capric acid, lauric acid, myristic acid,palmitic acid, stearic acid, behenic acid, melissic acid, palmitoleicacid, oleic acid, linolic acid, linolenic acid, arachidonic acid, erucicacid, 2-ethyl hexanoic acid, 2-hexyl decanoic acid, 2-heptyl undecanoicacid, 5, 7, 7-trimethyl-2-(1, 3, 3-trimethylbutyl)octanoic acid, methylbranched isostearic acid, cyclopentane carboxylic acid, cyclohexanecarboxylic acid, cholic acid, deoxycholic acid, glycyl lysine acid,benzoic acid, naphthoic acid, undecylenic acid or a tricyclic diterpenecarboxylic acid. Of these, resin acid residues such as tricyclicditerpene carboxylic acid, undecylenic acid which is a solid at ordinarytemperature, stearic acid or erucic acid are to be preferred, and resinacid residues of tricyclic diterpene carboxylic acids are particularlyto be preferred. As the resin acid residue of a tricyclic diterpenecarboxylic acid, the resin acid residue of rosin or hydrated rosin ispreferable. It may also be at least one carboxylic acid residue chosenfrom abietic acid, neoabietic acid, dihydroabietic acid, d-pimaric acid,iso d-pimaric acid, dihydroabietic acid, levopimaric acid, palustricacid, dextropimaric acid, sandarachpimaric acid, and their hydrates.

[0029] When the above makeup is used, there is no particular limitationon the weight average molecular weight of the aforesaid siliconecompound a) (formula 1), but 500-200000 and especially 1000-100000 areto be preferred.

[0030] The silicone compound a) of this invention may be synthesized bycarrying out an addition reaction of a main chain siloxane which is anorganohydrogen polysiloxane represented by the following general formula(5):

[0031] and a vinyl carboxylate to synthesize an alicyclic epoxy-modifiedsilicone, and reacting this with saturated or unsaturated carboxylicacids, especially tricyclic diterpene carboxylic acid (abbreviated asX-COOH in the following reaction equation) according to the followingreaction equation (6).

[0032] As the resin acid residue of a tricyclic diterpene carboxylicacid, the resin acid residue of rosin or hydrated rosin is preferable.It may also be at least one carboxylic acid residue chosen from abieticacid, neoabietic acid, dihydroabietic acid, d-pimaric acid, isod-pimaric acid, dihydroabietic acid, levopimaric acid, palustric acid,dextropimaric acid, sandarachpimaric acid, and their hydrates.

[0033] The addition reaction of the hydrogen silicone compound to thesingle-terminal vinyl silicone compound or vinyl alicyclic epoxide mayeasily be carried out in the presence of a platinum catalyst or rhodiumcatalyst. Moreover, the reaction of the alicyclic epoxy-denaturedsilicone and carboxylic acid does not require a catalyst, and thereaction can be carried out simply by heating.

[0034] In another method, a vinyl alicyclic epoxide is first reactedwith a tricyclic diterpene carboxylic acid, and an addition reactionwith a hydrogen silicone compound may then be performed to obtain theproduct.

[0035] As these reactions do not use an acid catalyst, polymerizationwith saturated or unsaturated carboxylic acids, and particularly withtricyclic diterpene carboxylic acids, does not occur.

[0036] Here, the organohydrogen polysiloxane may be straight chain orcyclic, and a branched compound as in general formula (3) is alsosuitable. The mixing ratio of this organohydrogen polysiloxane and vinylalicyclic epoxide is 0.5-1.5, and preferably 0.8-1.2, expressed as themole ratio of terminal unsaturated groups to SiH groups.

[0037] The above-mentioned addition reaction is preferably performed inthe presence of a platinum catalyst or a rhodium catalyst, suitableexamples being chloroplatinic acid, alcohol- denatured chloroplatinicacid and chloroplatinic acid-vinyl siloxane complex, etc. The catalystusage amount can be taken as the catalyst amount, which in terms ofplatinum or rhodium amount is 50 ppm or less, but more preferably 20 ppmor less. The above-mentioned addition reaction may be performed in anorganic solvent if necessary. Examples of this organic solvent arealiphatic alcohols such as methanol, ethanol, 2-propanol, and butanol,aromatic hydrocarbons such as toluene and xylene, aliphatic or aromatichydrocarbons such as n-pentane, n-hexane and cyclohexane, or halogenatedhydrocarbons such as dichloromethane, chloroform and carbontetrachloride.

[0038] The conditions of the above-mentioned addition reaction are notlimited, but the reaction may conveniently be carried out under refluxfor 1 to 10 hours.

[0039] The aforesaid reaction of the epoxy group and carboxylic acid iscompleted simply by heating at 60-200° C. in an organic solvent.Although an acid catalyst can also be used as a catalyst as it promotesthe reaction, a catalyst is not required if an alicyclic epoxy group isused as in this invention. As organic solvents, aromatic hydrocarbonssuch as toluene and xylene which have a high boiling point may be givenparticular mention. This reaction may conveniently be carried out underreflux for 1 to 20 hours.

[0040] The content of the silicone compound a) of this invention is0.1-99.5 weight %, but preferably 0.1-60 weight %. When this content isless than 0.1 weight % adhesion properties are insufficient, and if itexceeds 60 weight %. the desired makeup may not be obtained.

[0041] The following are examples of the oil b) which is a compositionalcomponent of this invention.

[0042] Examples of natural animal and vegetable fats and oils, andsemi-synthetic fats and oils, include avocado oil, linseed oil, almondoil, Chinese wax, perilla oil, olive oil, cacao butter, kapok wax, kayaoil, carnauba wax, liver oil, candellila wax, beef tallow, beef footoil, beef bone fat, hydrogenated beef tallow, apricot kernel oil,spermaceti, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil,rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter,Chinese tung oil, cinnamon oil, jojoba wax, shellac wax, turtle oil,soybean oil, tea seed oil, tsubaki oil, evening primrose oil, corn oil,lard, rape seed oil, Japanese tung oil, rice-bran wax, germ oil, horsefat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenatedcastor oil, caster oil fatty acid methyl ester, sunflower oil, grapeseed oil, bayberry wax, jojoba oil, macadamia nut oil, bees wax, minkoil, cottonseed oil, cotton wax, Japan wax, haze kernel oil, montan wax,coconut oil, hydrogenated coconut oil, tricoconut oil fatty acidglyceride, mutton-tallow, peanut oil, lanolin, liquid lanolin, reducedlanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fattyacid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolinalcohol acetate, lanolin fatty acid polyethylene glycol, POEhydrogenated lanolin alcohol ether, and egg yolk oil. Additionally, theterm “POE” as used herein stands for polyoxyethylene.

[0043] Examples of hydrocarbon oils include ozokerite, squalane,squalene, ceresine, paraffin, paraffin wax, liquid paraffin, pristane,polyisobutylene, microcrystalline wax and Vaseline; and those of ahigher fatty acid which can be mixed include lauric acid, myristic acid,palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid,linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid(EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearicacid.

[0044] Examples of higher alcohols include lauryl alcohol, myristylalcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecylalcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol,octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol,phytosterol, POE cholesterol ether, monostearyl glycerin ether (batylalcohol) and monooleyl glyceryl ether (cerakyl alcohol).

[0045] Examples of ester oils include diisobutyl adipate, 2-hexyldecyladipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates,isocetyl isostearate, trimethylolpropane triisostearic acid ester,ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate,trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritoltetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gumester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycoldicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amylacetate, ethyl acetate, butyl acetate, isocetyl stearate, butylstearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate,myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate,2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl12-hydroxystearate, dipentaerythritol fatty acid esters, isopropylmyristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristylmyristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate,N-lauroyl-L-glutaminic acid 2-octyldodecyl ester, diisostearyl malicacid, dextrin palmitic acid ester, dextrin stearic acid ester, dextrin2-ethylhexanic acid palmitic acid ester, cane sugar palmitic acid ester,cane sugar stearic acid ester, monobenzylidene sorbitol anddibenzylidene sorbitol.

[0046] Examples of glyceride oils include acetoglyceride, diisooctanoicacid glycride, triisostearic acid glyceride, triisopalmitic acidglyceride, tri-2-ethylhexanoic acid glyceride, monostearic acidglyceride, di-2-heptylundecanoic acid glyceride and trimyristic acidglyceride.

[0047] As examples of silicone oils, mention may be made of higheralkoxy-modified silicones such as dimethylpolysiloxane,methylphenyl-polysiloxane, methylhydrogenpolysiloxane,octamethylcyclotetrasiloxane, decamethylcyclopenta-siloxane,dodecamethylcyclohexasiloxane,tetramethyl-tetrahydrogencyclotetrasiloxane and stearoxysilicone, higherfatty acid-modified silicones, fluorine-modified silicones,amino-modified silicones, alkyl-modified silicones, higher fatty acidester-modified silicones, silicone resins and silicone rubbers.

[0048] As examples of fluorine-containing oils, mention may be made ofperfluoropolyether, perfluorodecalin and perfluorooctane.

[0049] One of more of these may be used as necessary.

[0050] It is preferable that these oils are liquid at ordinarytemperature, more preferable that they are organic powders having asilicone resin and/or silicone elastomer skeleton with a structuralrepeating unit of −[O—Si—] n−, and still more preferable that thesepowders partially have at least a fluorine group or an amino group.

[0051] The content of the oil b) in the makeup of this invention is0.5-99.9 weight %, preferably 0.5-95.0 weight %, and more preferably1.0-50.0 weight %. If this content is less than 0.5 weight %, the effectof the oil cannot be obtained, and if it exceeds 95.0 weight %, theeffect of the silicone compound a) of this invention (formula 1) maydiminish.

[0052] Examples of compounds having an alcoholic hydroxyl group in themolecular structure c) of this invention are ethanol, propanol, ethyleneglycol, ethylene glycol monoalkylether, diethylene glycolmonoethylether, polyethylene glycol, propylene glycol, dipropyleneglycol, 1,3-dibutylene glycol, glycerine, diglycerine, polyglycerine,pentaerythyrtol, cane sugar, lactose, xylitol, sorbitol, mannitol,maltitol, carrageenan, agar, agargum, dextrin, tragantogum, locust beangum, polyvinyl alcohol, polyoxyethylene polymers, polyoxyethylenepolyoxypropylene copolymers, hyarulonic acid, chondroitin sulfate,chitin and chitosan. One or more of these may be used as necessary, butcompounds which can dissolve the silicone compound a) of this invention(formula 1) are preferred.

[0053] It is preferred that the compound having an alcoholic hydroxylgroup is a water-soluble, monohydric or polyhydric alcohol, or awater-soluble polymer.

[0054] The content of the compound c) containing alcoholic hydroxylgroups in the makeup of this invention is 0.5-50.0 weight %. If it isless than 0.5 weight %, moisturizing properties, antimicrobialproperties and antibiological properties are insufficient, so it ispreferably 0.5-50.0 weight %. If it exceeds 50.0 weight %, tackinessincreases which is undesirable for a makeup material.

[0055] The makeup of this invention may also contain d) water as acompositional component. The water content in the makeup of thisinvention is 0-99.0 weight %, the blending proportion being increased ordecreased according to the form of the makeup.

[0056] An excellent makeup according to this invention may be obtainedfrom a) the silicone compound of this invention, b) an oil, c) acompound containing alcoholic hydroxyl groups and d) water, but e)powders and/or colorants, f) surfactants, g) cross-linkedorganopolysiloxanes and h) silicone resins, such as acryl/silicone graftor block copolymer, and silicone lattice compounds, etc., may also beadded if necessary.

[0057] e) Powders and/or colorants

[0058] Examples of a usable inorganic powder include titanium dioxide,zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, bariumsulfate, calcium sulfate, magnesium sulfate, calcium carbonate,magnesium carbonate, talc, mica, kaolin, sericite, muscovite, syntheticmica, phlogopite, ruby mica, biotite, lipidolite, silicic acid, silicicacid anhydride, aluminum silicate, magnesium silicate, aluminummagnesium silicate, calcium silicate, barium silicate, strontiumsilicate, metal salts of tungstic acid, hydroxyapatite, vermiculite,haidilite, bentonite, montmorillonite, hectorite, zeolite, ceramicspowder, calcium secondary phosphate, alumina, aluminum hydroxie, boronnitride and silica.

[0059] Examples of a usable organic powder include polyamide powder,polyester powder, polyethylene powder, polypropylene powder, polystyrenepowder, polyurethane powder, benzoguanamine powder,polymethylbenzoguanamine powder, polytetrafluoroethylene powder,polymethylmethacrylate powder, cellulose powder, silk powder, nylonpowder such as 12-nylon powder or 6-nylon powder, silicone powder,styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymerpowder, vinyl resin powder, urea resin powder, phenol resin powder,fluororesin powder, silicone resin powder, acrylic resin powder,melamine resin powder, epoxy resin powder, polycarbonate resin powder,microcrystalline fiber powder, starch powder and lauroyl lysine powder.

[0060] Examples of a usable surfactant metal salt powder (metal soappowder) include powders of zinc stearate, aluminum stearate, calciumstearate, magnesium stearate, zinc myristate, magnesium myristate, zinccetylphosphate, calcium cetylphosphate and zinc sodium cetylphosphate.

[0061] Examples of a usable colored pigment include inorganic redpigments, such as iron oxide, iron hydroxide and iron titanate;inorganic brown pigments, such as gamma-iron oxide; inorganic yellowpigments, such as iron oxide yellow and loess; inorganic black pigments,such as iron oxide black and carbon black; inorganic violet pigments,such as manganese violet and cobalt violet; inorganic green pigments,such as chromium hydroxide, chromium oxide, cobalt oxide and cobalttitanate; inorganic blue pigments, such as Prussian blue and ultramarineblue; lakes of tar pigments; lakes of natural dyes; and synthetic resinpowder complexes of the inorganic pigments as recited above.

[0062] Examples of a usable pearl pigment include titanium oxide-coatedmica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride,titanium oxide-coated talc, fish scales, and titanium oxide-coatedcolored mica; and examples of a usable metallic powder pigment includealuminum powder, copper powder and stainless powder.

[0063] Examples of a usable tar pigment include Red No. 3, Red No. 104,Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No.220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401,Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203,Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201,Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205,Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206 andOrange No. 207 (according to the pigment nomenclature method in JIS);and examples of a usable natural pigment include powders of carminicacid, laccaic acid, carthamin, bradilin and crocin.

[0064] The present silicone compounds are applicable to surfacetreatment of any powders so far as the powders can be used in generalcosmetic materials, irrespective of their shape (whether it isspherical, acicular or tabular), their size (whether it is fume, finegrain or pigment), and their structure (whether it is porous ornonporous) . It is preferred that part or all of the e) powder and/orcolorant is an organic powder having a silicone resin and/or siliconeelastomer skeleton with a structural repeating unit of −[O—Si—] n−.These powders may also be complexed and/or surface-treated with an oil,silicone or fluoride compound.

[0065] Furthermore, the present cosmetic materials can contain one ormore surfactants, if desired.

[0066] Examples of a usable anionic surfactant include saturated orunsaturated fatty acid soaps such as sodium stearate or triethanolaminepalmitate; alkyl ether carboxylic acids and salts thereof; salts ofamino acid-fatty acid condensates; amido ether carboxylic acid salts;alpha-sulfo fatty acid esters, alpha-acyl sulfonic acid; alkyl sulfonicacids; alkenesulfonicacids; sulfonated fatty acidesters; sulfonatedfatty acid amides; sulfonates of alkyl sulfonic acid salts and theirformaldehyde condensates; alkyl sulfonic acid ester salts; secondaryalcohol sulfates; alkyl and aryl ether sulfates; fatty acid ethersulfates, fatty acid alkylolamide sulfates; sulfate esters such asTurkey red oil; alkyl phosphates; alkenyl phosphates; ether phosphates;alkyl aryl ether phosphates; alkylamide phosphates; and active agents ofN-acylamino acid type.

[0067] Examples of a usable cationic surfactant include amine salts,such as alkylamine salts, polyamines and aminoalcohol fatty acidderivatives, quaternary alkylammonium salts, quaternary arylammoniumsalts, pyridinium salts and imidazolium salts.

[0068] Examples of a usable nonionic surfactant include sorbitan fattyacid esters, glycerin fatty acid esters, polyglycerin fatty acid esters,propylene glycol fatty acid esters, polyethylene glycol fatty acidesters, sucrose fatty acid esters, polyoxyethylene alkyl ethers,polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers,polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acidesters, polyoxyethylene sorbitol fatty acid esters, polyoxyethyleneglycerin fatty acid esters, polyoxyethylene propylene glycol fatty acidesters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castoroil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterolether, polyoxyethylene cholestanol ether, polyoxyethylene cholesterylether, polyoxyalkylene-modified organopoly-siloxanes,organopolysiloxanes modified with both polyoxyalkylene and alkyl groups,alkanolamides, sugar ethers and sugar amides.

[0069] Examples of a usable amphoteric surfactant include betaine,aminocarboxylates and imdazoline derivatives.

[0070] These surfactants are preferably modified silicones having apolyoxyalkylene chain in the molecule, and the HLB (hydrophilic lipidbalance) of these surfactants is preferably 2 -8.

[0071] g) Cross-linked organopolysiloxanes

[0072] The cross-linked organopolysiloxanes suitable for the presentcosmetic materials are those which cause swelling when they contain asilicone having a low viscosity of from 0.65 to 10.0 cs in a quantitylarger than their self weight. Further, it is desirable that thecross-linked structure of those organopolysiloxanes be formed byreaction between hydrogen atoms bonded directly to silicon atoms and across-linking agent having at least two vinylic reactive moieties permolecule. Furthermore, it is desirable in the foregoing reaction to usea cross-linking agent containing at least one moiety selected frompolyoxyalkylene, alkyl, alkenyl, aryl and fluoroalkyl moieties.

[0073] h) Silicone resins, such as acryl/silicone graft or blockcopolymers and silicone lattice compounds

[0074] It is preferred that the silicone resins of this invention areacryl silicones. It is moreover preferred that the silicone resins ofthis invention are acryl silicones containing at least one moietyselected from the group consisting of pyrrolidone, long-chain alkyl,polyoxyalkylene and fluoroalkyl moieties. The other favorable siliconeresins are silicone compounds having a lattice structure.

[0075] There is no particular limitation on the applications of themakeup of this invention, but examples include skin care products,hairdressing products, antiperspirant, makeup products and ultravioletdefense products. There is also no particular limitation on the form ofthe product, but it may be applied in liquid, emulsion, cream, solid,paste, gel, powder, laminate, mousse and spray forms.

[EXAMPLES]

[0076] This invention will now be described with reference to specificexamples, but the invention should not be construed as being limited tothese examples. Further, the term below [%] means [weight %] unlessotherwise specified.

[0077] EXAMPLE 1 (Synthesis of silicone compound)

[0078] 733 weight parts of organohydrogensiloxanes represented by thefollowing average structural formula (7):

[0079] and 1,000 weight parts of isopropyl alcohol were placed in areaction vessel, and 2 weight parts of a 0.5 weight % isopropyl alcoholsolution of chloroplatinic acid was added thereto. The reaction wascontinued for 6 hours under reflux of the solvent while dripping 70weight parts of 4-vinyl-1-cyclohexane-1,2-epoxide into the reactionvessel.

[0080] Then, the reaction mixture was heated under reduced pressure todistill off excess 4-vinyl-1-cyclohexane-1,2-epoxide and the solventtherefrom, which was replaced by 1000 weight parts of xylene. 165 weightparts of rosin (carboxy equivalent 330 g/mol) was added to the reactionliquor, and the reaction continued for 10 hours under reflux of thesolvent. This product was a light brown transparent liquid, viscosity215 cs (25° C.), specific gravity 1.013 (25° C.).

[0081] EXAMPLE 2 (Synthesis of silicone compound)

[0082] 768 weight parts of organohydrogensiloxanes represented by thefollowing average structural formula (8):

[0083] and 1,000 weight parts of isopropyl alcohol were placed in areaction vessel, and 2 weight parts of a 0.5 weight % isopropyl alcoholsolution of chloroplatinic acid was added thereto. The reaction wascontinued for 6 hours under reflux of the solvent while dripping 40weight parts of 4-vinyl-1-cyclohexane-1,2-epoxide into the reactionvessel. Then, the reaction mixture was heated under reduced pressure todistill off excess 4-vinyl-1-cyclohexane-1,2-epoxide and the solventtherefrom, which was replaced by 1000 weight parts of xylene. 330 weightparts of rosin (carboxy equivalent 330 g/mol) was added to the reactionliquor, and the reaction continued for 10 hours under reflux of thesolvent. This product was a light brown transparent liquid, viscosity600 cs (25° C.), specific gravity 0.987 (25° C.).

[0084] EXAMPLE 3 (Synthesis of silicone compound) 300 weight parts oforganohydrogensiloxanes represented by the, following average structuralformula (9):

[0085] and 1,000 weight parts of isopropyl alcohol were placed in areaction vessel, and 2 weight parts of a 0.5 weight % isopropyl alcoholsolution of chloroplatinic acid was added thereto. The reaction wascontinued for 6 hours under reflux of the solvent while dripping 70weight parts of 4-vinyl-1-cyclohexane-1,2-epoxide into the reactionvessel.

[0086] Then, the reaction mixture was heated under reduced pressure todistill off excess 4-vinyl-1-cyclohexane-1,2-epoxide and the solventtherefrom, which was replaced by xylene. 413 weight parts of rosin(carboxy equivalent 330 g/mol) was added to the reaction liquor, and thereaction continued for 10 hours under reflux of the solvent. Afterdistilling the reaction liquor under reduced pressure, a viscous, lightbrown transparent solid was obtained.

[0087] EXAMPLE 4 (Synthesis of silicone compound)

[0088] 300 weight parts of organohydrogensiloxanes represented by theaverage structural formula (9) and 1,000 weight parts of toluene wereplaced in a reaction vessel, and 2 weight parts of a 0.5 weight %toluene solution of chloroplatinic acid was added. The reaction wascontinued for 6 hours under reflux of the solvent while dripping 360weight parts of organopolysiloxane represented by the average structuralformula (10):

[0089] and was continued for a further 6 hours under reflux of thesolvent while dripping 105 weight parts of4-vinyl-1-cyclohexane-1,2-epoxide into the reaction vessel.

[0090] Then, the reaction mixture was heated under reduced pressure todistill off excess 4-vinyl-1-cyclohexane-1,2-epoxide and the solventtherefrom, which was replaced by xylene. 240 weight parts of rosin(carboxy equivalent 320 g/mol) was added to the reaction liquor, and thereaction continued for 16 hours under reflux of the solvent. Thereaction liquor was distilled off under reduced pressure to obtain theproduct. This product was a light brown transparent liquid, viscosity575 cs (25° C.), specific gravity 0.984 (25° C.).

[0091] An eyeliner was manufactured using the following ingredients inaccordance with the process described below: Manufacturing MethodIngredient Ratio (weight %) (1) Beeswax 5.0 (2) Cetyl alcohol 0.4 (3)Stearic acid 1.0 (4) Silicone compound obtained in Example 3 2.0 (5)Sesquioleic acid sorbitan 0.5 (6) Monooleic acid polyoxyethylenesorbitan 0.9 (7) Lecitin 0.1 (8) Black iron oxide 11.0  (9) Titaniumoxide 0.5 (10) Kaolin 0.5 (11) 1, 3-butylene glycol 6.5 (12) Antiseptics0.2 (13) Purified water Remainder (14) Silicic acid anhydride 0.6 (15)Alkali visocity-increasing 2.0 polymethacrylic acid polymer emulsion*(16) Triethanolamine 1.1 (17) Silicone acryl emulsion** 12.0 

[0092] Process 1: Components (1)-(10) are heated and homogenized in aroll mill.

[0093] Process 2: Components (11)-(16) are mixed.

[0094] Process 3: The product of step 1 is heated to 80° C., then theproduct of step 2 heated to 80° C. is poured in and emulsified.

[0095] Process 4: After cooling the product of process 3, component (17)is added to this.

[0096] The obtained eyeliner had good adhesive strength and was anexcellent eyeliner for makeup.

[0097] Embodiment 6 (Manufacture of Lip Cream)

[0098] A lip cream was manufactured using the following ingredients inaccordance with the process described below: Ingredient Ratio (weight%) 1) Polyethylene wax 4.0 2) Silicone compound obtained in Example 28.0 3) Vaseline 37.0  4) Starch fatty acid ester 7.0 5) Glycerine fattyacid ester 40.0  6) Partially cross-linked dimethylpolysiloxane* 3.0 7)Hydrophilic spherical silicic acid anhydride** 1.0

[0099] Manufacturing Method

[0100] The above components were dissolved and dispersed to melt fill aresin dish, and a lip cream was obtained.

[0101] The obtained lip cream was a lip cream which was excellent inadhesive strength to the lips, and had emollient properties.

[0102] Embodiment 7 (Manufacture of Mascara (Waterproof Type))

[0103] Mascara (waterproof type) was manufactured using the followingingredients in accordance with the process described below. IngredientRatio (weight %)  1. Carnauba wax 5.0  2. Micro crystalline wax 4.0  3.Silicone resin (MQ resin) 3.0  4. Silicone compound obtained in Example1 10.0   5. Dextrin fatty acid ester 5.0  6. Denatured clay mineral 2.0 7. Propylene carbonate 0.6  8. Silicic acid anhydride 1.0  9. PigmentSuitable amount 10. Light liquid paraffin Remainder

[0104] Manufacturing Method

[0105] Components 1-10 were dissolved by heating, and mixed anddispersed with three rollers to obtain a mascara.

[0106] The stability of the obtained mascara was good, it had smoothspreadability, and an excellent feel.

[0107] Embodiment 8 (Manufacture of Mascara (W/O type))

[0108] Mascara (W/O type) was manufactured using the followingingredients in accordance with the process described below. ingredientRatio (weight %)  1. Carnauba wax 4.0  2. Beeswax 4.0  3. Siliconecompound obtained in Example 4 2.0  4. Behenyl alcohol 1.5  5. Acrylsilicone* 3.0  6. Cane sugar fatty acid ester 1.5  7. Sesquioleic acidsorbitan 2.0  8. Monooleic polyoxyethylene 1.0 sorbitan (20E.O.)  9.Surface-treated single crystal titanium oxide 2.0 10. Perfluoroalkylgroup-containing 8.0 ester processed black iron oxide 11. Mica 6.0 12.Purified water Remainder 13. Sodium hydroxide 0.5 14. 1, 3-butyleneglycol 8.0 15. Antiseptics Suitable Quantity 16. Polyacrylic acid alkylwater dispersion 30.0  17. Nylon terminals 4.0 18. Cosmetics componentsSuitable Quantity 19. Perfume Suitable Quantity

[0109] Manufacturing Method

[0110] A: Components 1-4 are heat fused at 100° C., then components 5-7are added and dissolved. Components 8-10 are added, and thoroughly mixedto disperse the powders at 75° C.

[0111] B: Components 11-17 are heat fused at 75° C.,

[0112] C: B is added to A to make an emulsion. This is then degassed,cooled, and component 18 is added to obtain the mascara.

[0113] The obtained mascara had good color, adhesive strength toeyelashes, and was an excellent mascara for long-term makeup.

[0114] Embodiment 9 (Manufacture of Emulsion Type Foundation)

[0115] The emulsion type foundation was manufactured using the followingingredients in accordance with the process described below. IngredientRatio (weight %) Oil phase (1) Octamethylcylotetrasiloxane 10.0  (2)Siliconated cellulose 2.0 (3) Silicone compound obtained in Example 45.0 (4) Di-isooctanoic acid neo pentyl glycol 5.0 (5) Squalane 2.5 (6Tri-isooctanoic acid glycerol 2.0 Powder fraction (7) Siliconized talc7.0 (8) Siliconized titanium dioxide 12.0  (9) Siliconized silicic acidanhydride 2.0 (10) Silicone powder* 4.0 (11) Siliconized color pigment2.0 Aqueous phase (12) 1, 3-butylene glycol 10.0  (13) Ethanol 7.0 (14)Purified water Remainder

[0116] Manufacturing Method

[0117] After stirring the aqueous phase, the powder fraction was addedand processed in a homomixer. The oil phase which had been dissolved wasadded, processed in the homomixer, and cooled to give a foundation.

[0118] The obtained emulsion type foundation was excellent in adhesivestrength, and was excellent in durability of the makeup effect.

[0119] [Advantages of the Invention]

[0120] The silicone compound of this invention can be synthesizedsimply. As an acid catalyst is not needed, safety is also high and it issuitable for blending with makeup. The makeup with which this siliconecompound is blended does not have oiliness, is excellent in an adhesivestrength, has excellent makeup retention, and also has very goodstability in that is unaffected by temperature and time.

What is claimed is:
 1. A silicone compound represented by the generalformula (1): R ¹ _(a) R ² _(b) SiO _((4—a—b)/2) (in the formula, R¹ isat least one substituent group having 1-30 carbon atoms chosen fromalkyl aryl, aralkyl, fluorine-substituted alkyl ororganopolysiloxanylsilyl, R² is a carboxylate residue represented by thefollowing general formula (2):

R³ is a saturated or unsaturated hydrocarbon group having 2-30 carbonatoms, a is 1.0-2.5, and b is 0.001-1.5).
 2. A silicone compound asdefined in claim 1, wherein R³ is a tricyclic dipertene carboxylic acidresidue.
 3. A silicone compound as defined in claim 1, wherein at leastpart of R¹ is represented by the following general formula (3):

(in the formula, R⁴may respectively be identical or different, and is atleast one substituent group having 1-30 carbon atoms chosen from alkyl,aryl, aralkyl, fluorine-substituted alkyl or hydroxyl, c is 1-5, and dis 0-500).
 4. A silicone compound as defined in claim 2, wherein atleast part of R¹ is represented by the following general formula (3):

(in the formula, R⁴ may respectively be identical or different, and isat least one substituent group having 1-30 carbon atoms chosen fromalkyl, aryl, aralkyl, fluorine-substituted alkyl or hydroxyl, c is 1-5,and d is 0-500).
 5. A makeup comprising 0.1 to 99.5 weight % of a) asilicone compound as defined in claim 1, and b) 0.5 to 99.9 weight % ofan oil.
 6. A makeup comprising 0.1 to 99.5 weight % of a) a siliconecompound as defined in claim 2, and b) 0.5 to 99.9 weight % of an oil.7. A makeup comprising 0.1 to 99.5 weight % of a) a silicone compound asdefined in claim 3, and b) 0.5 to 99.9 weight % of an oil.
 8. A makeupas defined in claim 5, further comprising c) 50 weight % or less of acompound having alcoholic hydroxyl groups in the molecular structure. 9.A makeup as defined in claim 8, further comprising d) 99.0 weight % orless of water.
 10. A makeup as defined in claim 9, further comprising e)a powder and/or a colouring agent.
 11. A makeup as defined in claim 9,further comprising f) a surfactant.
 12. A makeup as defined in claim 9,further comprising g) a cross-linked organopolysiloxane.
 13. A makeup asdefined in claim 9, further comprising h) silicone resin.
 14. A skincare product, of which at least part is a makeup as defined in claim 9.15. A hairdressing product, of which at least part is a makeup asdefined in claim
 9. 16. An antiperspirant, of which at least part is amakeup as defined in any of claim
 9. 17. A makeup product, of which atleast part is a makeup as defined in any of claim
 9. 18. An ultravioletdefense product, of which at least part is a makeup as defined in claim9.
 20. A makeup as defined in claim 14, which is a liquid, emulsion,cream, solid, paste, gel, powder, laminate, mousse or spray.
 21. Amakeup as defined in claim 15, which is a liquid, emulsion, cream,solid, paste, gel, powder, laminate, mousse or spray.
 22. A makeup asdefined in claim 16, which is a liquid, emulsion, cream, solid, paste,gel, powder, laminate, mousse or spray.
 23. A makeup as defined in claim17, which is a liquid, emulsion, cream, solid, paste, gel, powder,laminate, mousse or spray.
 24. A makeup as defined in claim 18, which isa liquid, emulsion, cream, solid, paste, gel, powder, laminate, mousseor spray.
 25. A method of manufacturing a silicone compound as definedin claim 1, wherein an alicyclic epoxy-modified silicone is synthesizedby an addition reaction of a main chain siloxane which is anorganohydrogen polysiloxane to a vinyl alicyclic epoxide, and asaturated or unsaturated carboxylic acid is reacted therewith.
 26. Amethod of manufacturing a silicone compound as defined in claim 2,wherein an alicyclic epoxy-modified silicone is synthesized by anaddition reaction of a main chain siloxane which is an organohydrogenpolysiloxane to a vinyl alicyclic epoxide, and a saturated orunsaturated carboxylic acid is reacted therewith.
 27. A method ofmanufacturing a silicone compound as defined in claim 3, wherein analicyclic epoxy-modified silicone is synthesized by an addition reactionof a main chain siloxane which is an organohydrogen polysiloxane to avinyl alicyclic epoxide, and a saturated or unsaturated carboxylic acidis reacted therewith.